Insecticidal methods and compositions utilizing ketone adducts



ted States Patent 3,469,010 INSECTICIDAL METHODS AND COMPOSITIONSUTILIZING KET ONE ADDUCTS Pasquale LOIlIlbZlI'dO, East Hanover Township,Morris County, N.J., assignor to Allied Chemical Corporation, New York,N.Y., a corporation of New York No Drawing. Original application Mar.19, 1963, Ser. No. 266,215. Divided and this application Dec. 15, 1966,Ser. No. 619,096

Int. Cl. A01n 9/02 lU.S. Cl. 424-311 10 Claims ABSTRACT OF THEDISCLOSURE Use of adducts of decachlorooctahydro-l,3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one and other ketones as insecticides.

This is a division of application Ser. No. 266,215, filed Mar. 19, 1963,now abandoned. The invention relates to new adducts prepared from theketone, decachloroctahydro-1,3,4-metheno-2H-cyclobuta (cd)pentalen-Z-one, to new pesticidal compositions containing adducts ofsaid ketone and to a method of cornbatting pests, especially insects,with these new pesticidal compositions.

Decahlorooctehydro-1,3,4-metheno2H-cyclobuta (cd) pentalen-Z-one,hereafter referred to as polycyclic ketone, is a complex chlorinatedpolycyclic ketone having the molecular formula C Cl O and a molecularWeight of 490.68. It is believed to be most accurately represented bythe following cage structural formula:

This polycyclic ketone may be prepared in known manner by hydrolyzingthe reaction product of hexachlorocyclopentadiene and sulfur trioxide.

An object of the present invention is to provide new ketone adductsexhibiting high pesticidal activity.

Another object of the invention is to provide new pesticidalcompositions containing the ketone adducts as active ingredients.

Still another object of the invention is to provide a method forcombatting pests, especially insects, comprising contacting the pestswith pesticidal compositions containing the ketone adducts as activeingredients.

It is a further object of the invention to provide a simple andeconomical method for preparing the ketone adducts.

Other objects and advantages of the invention will be apparent from thefollowing description.

The ketone adducts contemplated by this invention comprise thoseobtained by reacting the polycyclic keton with a ketone having a generalformula selected from the group consisting of (1) RCH COR in which R isa member of the group consisting of hydrogen and methyl and R is amember of the group consisting of alkyl, aryl and acyl radicals,

3 09,010 Patented Sept. 23, 1969 ICE in which R is a member of the groupconsisting drogen and alkyl radicals and of hyin which R is a member ofthe group consisting drogen and alkyl radicals.

In the compounds having the general formula RCH COR the alkyl and arylradicals represented by R may be substituted or unsubstituted. Thesubstituted alkyl radicals include, but are not limited to, arylalkyl,haloalkyl and carboalkoxyalkyl. The unsubstituted alkyl radicalspreferably contain 1 to 9 carbon atoms, while the alkyl portion of thesubstituted alkyl radicals preferably contains 1 to 4 carbon atoms. Thealkoxy portion of the carboalkoxyalkyl radicals also preferably contains1 to 4 carbon atoms. Among the compounds in this category are2-octanone, 2-nonanone, 2-heptanone, Z-undecanone, acetone,4-methyl-2-pentanone, 3-pentanone, Z-butanone, Z-pentanone, diacetyl,chloroacetone phenylacetone, acetophenone, 3-methyl-2-butanone, ethyllevulinate, ethyl pyruvate, butyl levulinate, methyl pyruvate, etc.

In the compounds represented by the general formula of hythe alkylradical preferably contains 1 to 3 carbon atoms. Compounds in thiscategory include cyclopentanone, 2- methyl-cyclopentanone,3-methylcyclopentanone, 4-methylcyclopentanone, etc.

In the group of compounds represented by the general formula the alkylradical preferably contains 1 to 3 carbon atoms. Compounds in thiscategory include cyclohexanone, 2- rnethvlvclohexanone.3-methylcyclohexanone. etc.

The ketone adducts of the invention may be prepared in simple andeconomical manner by reacting the polycyclic ketone with the desiredketone, in mol ratio of about 0.5 to 2 mols of polycyclic ketone per molof ketone, at temperature ranging from room temperature to about 250 C.

If the ketone is available in hydrate form, it can be dehydrated beforereaction by heating it in an oven at temperature of about to C. or byrefluxing it with an aromatic solvent such as xylene to remove theWater. The water can also be removed during reaction, as describedbelow.

Although the reactants may be employed in mol ratio of about 0.5 to 2mols of polycyclic ketone per mol of ketone, it is preferred to useapproximately equimolar proportions of the reactants.

The reaction is carried out at room temperature to about 250 C., usuallyat room temperature of about 55 to 200 C. The reaction temperature ispreferably the flux temperature of the reaction mixture.

If desired, the reaction may be carried out in the presence of anorganic solvent. The solvent must be inert to the reactants and thedesired ketone adduct. Among the suitable solvents are aliphatic oraromatic hydrocarbons such as xylene, toluene, benzene, petroleum ether,methylene chloride, etc. The solvent serves to keep the adduct insolution. Moreover, if the polycyclic ketone 1s empolyed in hydrateform, the solvent enables dehydration thereof during the reaction.

The ketone adducts may be recovered from the react on mixture byprocedures known in the art, as by precip tation with a non-solvent,e.g. hexane, followed by filtration and drying. Th adducts may bepurified, for example, by recrystallization from hexane.

The following examples are typical of preparatlon of the ketone adductsof this invention. In the examples, parts are by weight.

Example 1 56 parts of polycyclic ketone hydrate (4 mols H O) weredissolved in 79 parts of acetone, filtered to remove a small amount ofinsoluble material and then distilled to a pot temperature of 85 C.Since acetone boils at 56 (3., most of the unreacted acetone was removedThe remaining unreacted acetone was removed by stripp ng n vacuo. Thisprocedure was repeated twice, resulting 1n production of 53 parts ofsolid polycyclic ketone-acetone adduct (96% yield).

The adduct melted at 342348 C. with decomposltion, and its infraredspectrum showed hydroxyl absorption at 2.78 microns and carbonylabsorption at 5.85 microns.

Example 2 56 parts of polycyclic ketone hydrate (4 mols H parts of4-methyl-2-pentanone and 260 parts of toluene were mixed and refluxed.The water formed was azeotroped out of the reaction mixture over aperiod of hours. Solvent was removed by distillation in vacuo, leaving50 parts of solid polycyclic ketone-4-methyl-2-pentanone adduct.

The adduct melted at 160l65 C., and its infrared spectrum showedhydroxyl absorption at 2.78 microns and carbonyl absorption at 5.86microns.

Example 3 56 parts of polycyclic ketone hydrate (4 mols H O) were mixedwith 215 parts of xylene, and the mixture was refluxed. The water formedwas azeotroped out of the mixture over a period of 3 hours. 14.4 partsof ethyl levulinate were then added to the solution, and the mixture wasrefluxed for 18 hours. The solution was filtered and the filtratestripped of solvent in vacuo to yield a viscous oil. Trituration of theoil with hexane gave 38 parts (60% yield) of solid polycyclicketone-ethyl levulinate adduct.

The adduct had a melting point of 748l C., and its infrared spectrumshowed hydroxyl absorption at 2.98 microns and carbonyl absorption at5.80 and 5.88 microns.

Example 4 56 parts of polycyclic ketone (4 mols H O) were refluxed with225 parts of xylene to azeotropically remove water. 17 parts ofcyclopentanone were added to the xylene solution, and the mixture wasrefluxed overnight. The solution was then filtered to remove insolublematerial and stripped to yield an oil. The oil was triturated withhexane to give 37 parts (64% yield) of solid polycyclicketone-cyclopentanone adduct.

The adduct was recrystallized from hexanemethylene chloride mixture toproduce a purified product having a melting point of 195-197 C. Theinfrared spectrum of the adduct showed hydroxyl absorption at 2.96microns, carbon-hydrogen absorption at 3.34, 3.44, 6.88 and 7.12 micronsand carbonyl absorption at 5.77 microns.

4 Example 5 Polycyclic ketone-2-nonanone adduct was prepared by theprocedure described in Example 5. 44 parts of solid adduct, constitutinga yield of were obtained.

The adduct had a melting point of 70-76" C., and its infrared spectrumshowed hydroxyl absorption at 2.96 microns and carbonyl absorption at5.88 microns.

Example 7 Polycyclic ketone-Z-heptanone adduct was prepared by themethod described in Example 5. 27 parts of solid adduct were initiallyobtained, and an additional 11 parts of adduct were obtained byrefreezing the filtrate. The total crop constituted a yield of 63%.

The adduct was recrystallized from hexanemethylene chloride mixture toproduce a purified product melting at -86 C. The infrared spectrum ofthe adduct showed hydroxyl absorption at 2.95 microns, carbon-hydrogenabsorption at 3.39, 3.47, 6.85, 7.01 and 7.15 microns and carbonylabsorption at 5.87 microns.

Example 8 Polycyclic ketone-Z-undecanone adduct was prepared by theprocedure described in Example 5. A total of 38 parts of solid adductwere obtained in two crops, representing a 50% yield.

The adduct had a melting point of 68-71 C., and its infrared spectrumshowed hydroxyl absorption at 3.00 microns and carbonyl absorption at5.90 microns.

Example 9 56 parts of polycyclic ketone hydrate (4 mols H O) were mixedwith 82 parts of 3-pentanone. Insoluble material was filtered off, andthe mixture was heated for two hours and then stripped in vacuo. 51parts of solid polycyclic ketone-B-pentanone adduct were obtained.

The adduct had a melting point of 344348 C. with decomposition, and itsinfrared spectrum showed hydroxyl absorption at 2.90 microns andcarbonyl absorption at 6.00 microns.

Example 10 56 parts of polycyclic ketone hydrate (4 mols H O) were mixedwith 81 parts of Z-butanone. The mixture was boiled down on a steam bathfour times to obtain a product comprising solid polycyclicketone-Z-butanone adduct.

The adduct had a melting point of 346350 C. with decomposition, and itsinfrared spectrum showed hydroxyl absorption at 2.90 microns andcarbonyl absorption at 5.86 and 5.99 microns.

Example 11 56 parts of polycyclic ketone hydrate (4 mols H O) were mixedwith 49 parts of Z-pentanone, and the mixture was heated at reflux for 4hours. Excess Z-pentanone was stripped off. Additional 2-pentanone wasadded, and the mixture was heated to C. and then stripped in vacuo. 51parts of solid polycyclic ketone-Z-pentanone adduct were obtained.

The adduct had a melting point of 84l60 C. and its infrared spectrumshowed hydroxyl absorption at 2.90 microns and carbonyl absorption at5.85 and 5.98 microns.

Example 12 56 parts of polycyclic ketone hydrate (4 mols H O) were mixedwith 20 parts of cyclohexanone. 172 parts of xylene were added to themixture, and the water formed was azeotroped out. The mixture was heatedat 120 C. for several hours and then stripped in vacuo. An additional 20parts of cyclohexanone and 43 parts of xylene were added, and themixture was heated for hours at 150 C. The mixture was then stripped invacuo to a small volume. Partial crystallization occurred, and parts ofsolid polycyclic ketone-cyclohexanone adduct were obtained.

The adduct had a melting point of 166171 C., and its infrared spectrumshowed hydroxyl absorption at 3.02 microns and carbonyl absorption at5.88 microns.

Example 13 56 parts of polycyclic ketone hydrate (4 mols H O) wereazeotroped free of water in xylene. 8.6 parts of diacetyl were thenadded, and the mixture was refluxed overnight. Solvent was stripped fromthe mixture in vacuo to yield a viscous solid. The solid was boiled upwith hexane, filtered and washed with hexane. 42 parts of solidpolycyclic ketone-diacetyl adduct were obtained.

The adduct had a melting point of 122-350 C. with decomposition, and itsintrared spectrum showed hydroxyl absorption at 2.80 microns andcarbonyl absorption at 5.65 and 5.75 microns.

Example 14 56 parts of polycyclic ketone hydrate (4 mols H O) wereazeotroped free of water in 215 parts of xylene. 9.3 parts ofchloroacetone were then added, and the mixture was refluxed overnight.Solvent was stripped from the mixture in vacuo, and the resultant solidwas triturated with hexane and filtered oft. An additional 10 parts ofchloroacetone were added to the solid along with 172 parts of xylene.The hexane and water were distilled off, and the mixture was refluxedovernight. Solvent was stripped in vacuo, and the resultant solid wasboiled up with hexane, filtered 011 and washed with hexane. 37 parts(64% yield) of solid polycyclic ketone-chloroacetone adduct wereobtained.

The adduct had a melting point of 145152 C., and its innfrared spectrumshowed hydroxyl absorption at 2.80 microns and carbonyl absorption at5.76 microns.

Example 15 56 parts of polycyclic ketone hydrate (4 mols H O) wereazeotroped free of water in 215 parts of xylene. 13.5 parts ofphenylacetone were added to the mixture, and it was refluxed for 60hours. Solvent was stripped from the mixture in vacuo to yield an oilwhich solidified overnight. The solid was triturated with hexane,filtered off and washed with hexane. 42 parts (67% yield) of solidpolycyclic ketone-phenylacetone adduct were obtained.

The adduct exhibited a melting point of 140-143 C., and its infraredspectrum showed hydroxyl absorption at 2.93 microns and carbonylabsorption at 5.87 microns.

Example 16 56 parts of polycyclic ketone hydrate (4 mols H O) wereazeotroped free of water in 215 parts of xylene. 12 parts ofacetophenone were added, and the mixture was refluxed overnight. Themixture was filtered and then stripped of solvent in vacuo to yield asolid. The solid was triturated with hexane, filtered off and washedwith hexane. 51.5 parts (84% yield) of solid polycyclicketoneacetophenone adduct were obtained.

The adduct was recrystallized from hexane-methylene chloride mixture toproduce a purified product having a melting point of 152l53 C. Theinfrared spectrum of the adduct showed hydroxyl absorption at 2.95microns, carbon-hydrogen absorption at 3.23 and 3.41 microns, carbonylabsorption at 5.98 microns and aromatic ring vibrations at 6.25, 6.31and 6.89 microns.

6 Example 17 56 parts of polycyclic ketone hydrate (4 mols H O) wereazeotroped free of water in 259 parts of xylene. 8.6 parts of3-methyl-2-butanone were added, and the mixture was refluxed overnight.The solution was filtered and then stripped of solvent in vacuo. An oilresulted which solidified upon trituration with hexane. The solid wasfiltered oil and washed with hexane. 36 parts (62% yield) of solidpolycyclic ketone-3-methyl-2-butanone adduct were obtained.

The adduct exhibited a melting point of 139-143" C., and its infraredspectrum showed hydroxyl absorption at 3.01 microns and carbonylabsorption at 5.92 microns.

Example 18 56 parts of polycyclic ketone hydrate (4 mols H O) wereazeotroped free of water in 215 parts of refluxing xylene. 13 parts ofethylacetoacetate Were added, and the mixture was heated at 100 C. for40 hours. The resulting mixture was filtered, and the filtrate wasstripped of solvent in vacuo to yield 59 parts yield) of a viscous, darkbrown oil constituting polycyclic ketone-ethylacetoacetate adduct.

The infrared spectrum of the adduct showed hydroxyl absorption at 2.98microns and carbonyl absorption at 5.80 and 5.88 microns.

Example 19 56 parts of polycyclic ketone hydrate (4 mols H O) wereazeotroped free of water in 215 parts of refluxing xylene. 16 parts oftert.-butylacetoacetate were added, and the mixture was heated at 110 C.overnight. The mixture was then stripped of solvent in vacuo to produce62 parts of a viscous, dark oil comprising polycyclicketonetert.-butylacetoacetate adduct.

The infrared spectrum of the adduct showed hydroxyl absorption at 2.93microns and carbonyl absorption at 5.74 and 5.87 microns.

Example 20 49 parts of anhydrous polycyclic ketone and 12 parts of ethylpyruvate were allowed to react in refluxing toluene over a period of 4/2 days. Solvent was stripped from the mixture in vacuo to obtain aslightly oily solid. The solid was triturated with hexane, filtered offand washed with hexane to obtain 38 parts of air-dried solid comprisingpolycyclic ketone-ethyl pyruvate adduct. The adduct was recrystallizedfrom 60 parts of chloroform to obtain 12 parts of purified adduct havinga melting point of 240- 247 C. Additional adduct was obtained by boilingdown the filtrate and allowing it to crystallize.

The infrared spectrum of the adduct showed hydroxyl absorption at 2.92microns and carbonyl absorption at 5.63 and 5.93 microns.

Example 21 49 parts of anhydrous polycyclic ketone were prepared byazeotropically distilling water out of ketone hydrate (4 mols H O) usingtoluene. 17.2 parts of butyl levulinate were added, and the mixture wasrefluxed overnight. Solvent was stripped in vacuo to yield an oilysolid. The solid was triturated with hexane, filtered off and washedwith hexane. The solid and filtrate were then combined. 176 parts ofxylene were added, and solvent was removed to a pot temperature of C.The resulting mass was then allowed to reflux for a few days. Solventwas then stripped from the mass in vacuo to obtain a dark oil. The oilwas dissolved in a small amount of hot hexane and cooled. 45 parts (68%yield) of solid polycyclic ketone-butyl levulinate crystallized out.

The adduct exhibited a melting point of 94-96" C. afterrecrystallization from hexane-methylene chloride mixture. The infraredspectrum of the adduct showed hydroxyl absorption at 2.91 microns andcarbonyl absorption at 5.77 and 5.87 microns.

3,469,010 7 8 Example 22 The wettable powder compositions can readily beprepared by mixing or milling the active ingredient with the carrier andwetting agent to a typical particle size of from about 3 to 40 microns.The composition is admixed with water to form an aqueous dispersionsuitable for spraying containing about 0.001 to 0.1% by Weight of activeingredient.

Representative solid carriers which may be used in preparing thewettable powders include magnesium and aluminum silicates (talc, kaolinclays, attapulgite clays, etc.), carbonates (dolomite, chalk, etc.),materials containing silicic acid (diatomaceous earth), fullers earth.gypsum, sulfur, etc.

The dosage of the active ingredient depends on the 15 particularorganisms to be controlled, field conditions.

53 parts of polycyclic ketone hydrate (4 mols H O) were azeotroped freeof water in 172 parts of refluxing xylene. 10 parts of methyl pyruvatewere added, and the mixture was refluxed for 41 hours. Insolublematerial was filtered off, and the filtrate was stripped of solvent invacuo. A semi-solid was obtained which was triturated with hexane,cooled, filtered oif and washed with hexane. 42 parts of solidpolycyclic ketone-methyl pyruvate were obtained. 10

The adduct was recrystallized from chloroformmethylene chloride mixtureto obtain a purified product having a melting point of 248-25 1 C. Theinfrared spectrum of the adduct showed hydroxyl absorption at 2.92microns and carbonyl absorption at 5.62 and 5.92 microns.

The ketone adducts of this invention may be applied as known in the In yevent, sufficient quantity to pests, especially insects, 3515 but; argadvantageously Of the active ingredient iS used t provide the desiredincorporated as ingredients in suitable liquid or solid cartoxicity.riers to provide pesticidal spray or dust compositions. Exemplary testsof the ketone adducts of the present The liquid pesticidal compositionsgenerally contain in invention are set forth below:

Percent Kill Mexican Bean Beetle Southern Active Ingredient FormulatorLarvae Annyworms Polycyclic ketone-cyclopcutanonc adduct 2 pounds activeingredient per 100 gallons water 100 .00 Polycyclic ketone-.Z-octanoneadduct c r (l \Jl) Polycyclic ketone-2-uouauone adduct 2 c ll Polycyclicketone-2-heptanone adduct- 00 Polycyclic ketone-acetone adduct it!)Polycyclic ketone-4nietltyl-2pe1itaone adduct. 00 Polycyclickctone-3-pentanone adduct 100 Polycyclic ketoue-Z-butanone adduct lit)Polycyclic ketone-Z-pcut-anonc adduct. no Polycyclicketone-cyclohcxauone adduct" 00 Polycyclic ketone-diacetyl adduct .000Polycyclic ketone-chloroacetone adduct. 00 Polycyclicketone-phenylacetonc adduct it) Polycyclic ketone-acetophenone adduct.00 Polycyclic kctone-3-methyl-2-butanone l 00 Polycyclic ketone-ethyllevulinate adduct).-- 00 Polycyclic ketone-ethylacetoacetate adduct 1.00Polycyclic ketone-tert.-butylacetoacetate adduct 8 pounds wettablepowder composition 1 per 100 gallons water r 100 100 Polycyclicketone-ethyl pyruvate adduct 2 pounds active ingredient per 100 gallonsacetone-water solution (111) lDO Polycyclic ketone-butyl levulinateadduct r do 100 ill!) Polycyclic ketone-methyl pyruvate adduct do 80 0 125.0% active ingredient, 73.5% Attaclay (attapulgite clay carrier),0.75% Elvanol 51-05 (water-soluble synthetic polyvinyl alcoholdispersing gent), 0.75% N acconol SW (alkyl aryl sulionate wettingagent).

proportions by weight about to of the adduct The tests on toxicity toMexican bean beetle larvae as active ingredient, about 6 5 to 88% of anaromatic sol- (Epilachmz va-rivestis) were carried out by sprayinghortivent and about 2 to 10% of a suitable Wetting or emulsifycultural(cranberry) bean plants with the indicated ing agent, such as diglycololeate, p-isooctyl phenyl ether formulation and allowing the plants todry. The larvae of polyethylene glycol, blends of alkyl aryl polyetheralcowere confined to the treated foliage by means of wire hols withalkyl aryl sulfonates and blends of polyoxyethyl- 55 cages. Record ofkill was made 3 days after treatment. ene sorbitan esters of mixed fattyand resin acids with The tests on Southern armyworms (Prodenia eridania)alkyl aryl sulfonates. The resulting concentrate solution is werecarried out by spraying horticultural (cranberry) diluted or admixedwith water to form an aqueous disbean plants with the indicatedformulation and allowing persion or emulsion suitable for sprayapplication containthe plants to dry. The armyworms were confined to theing about 0.001 to 0.1% by weight of active ingredient. a d foliage ymeans of Wire g Mortality count Representative aromatic solvents whichmay be used in was made three days after treatment. preparing the liquidpesticidal compositions include xy- Iclaim: lene, high aromaticsolvents, methylated naphthalenes, 1. An insecticidal compositioncomprising an insectiheavy aromatic naphtha, etc. It is an advantage ofthis cidally effective amount of an adduct prepared by reacinventionthat the adducts have substantially greater solution ofdecachlol'ooctahydfo-1,3,4-1'I1ethe110-2H-CYC10bum bility in aromaticsolvents than the polycyclic ketone pentalen-z-one and a Compound havinga formula per e, selected from the group consisting of The wettablepowder compositions generally contain RcHzcoR1 in Which R is a member ofthe group in proportions by weight about 25 to 75% of the activeconsisting of hydrogen and methyl and R is a memingredient, about 20 to73% of a finely'divided solid carher of the group consisting ofunsubstituted alkyl Tier and about 2 to 5% of suitable wetting anddispersing containing 1 to 9 carbon atoms, aryalkyl in which agents.Typical wetting agents include polyether sulthe alkyl contains 1 to 4carbon atoms, haloalkyl fonates, alkyl aryl sulfonates, etc. Typicaldispersing agents in which the alkyl contains 1 to 4 carbon atoms.include ligninsulfonates, naphthalene sulfonic acid-formcarboalkoxyalkylin which the alkyl contains 1 to 4 aldehyde condensates, etc. 75 carbonatoms and the alkoxy contains 1 to 4 carbon atoms, carboalkoxy in whichthe alkoxy contains 1 to 2 carbon atoms, phenyl and acetyl,

in which R is a member of the group consisting of hydrogen and alkylcontaining 1 to 3 carbon atoms and in which R is a member of the groupconsisting of hydrogen and alkyl containing 1 to 3 carbon atoms, in molratio of about 0.5 to 2 mols ofdecachlorooctahydro-1,3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one permol of compound, at temperatures ranging from room temperature to about250 0., together with a liquid or solid insecticidal carrier therefor.

2. An insecticidal composition comprising an insecticidally eflectiveamount of an adduct prepared by reaction ofdecachlorooctahydro-1,3,4-metheno-2l-I-cyclobuta (cd) pentalen-2-one anda compound having the formula RCH COR in which R is a member of thegroup consisting of hydrogen and methyl and R is a member of the groupconsisting of unsubstituted alkyl containing 1 to 9 carbon atoms,arylalkyl in which the alkyl contains 1 to 4 carbon atoms, haloalkyl inwhich the alkyl contains 1 to 4 carbon atoms, carboalkoxyalkyl in whichthe alkyl contains 1 to 4 carbon atoms and the alkoxy contains 1 to 4carbon atoms, carboalkoxy in which the alkoxy contains 1 to 2 carbonatoms, phenyl and acetyl, in mol ratio of about 0.5 to 2 mols ofdecachlorooctahydro-1,3,4- metheno-ZH-cyclobuta (cd) pentalen-Z-one permole of compound, at temperature ranging from room temperature to about250 C., together with a liquid or solid insecticidal carrier therefor.

3. An insecticidal composition comprising an insecticidally eflfectiveamount of an adduct prepared by reac tion ofdecachlorooctahydro-1,3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one and acompound having the formula in which R is a member of the groupconsisting of hydrogen and alkyl containing 1 to 3 carbon atoms, in molratio of about 0.5 to 2 mols of decachlorooctahydro-l,3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one per mol of compound, attemperature ranging from room temperature to about 250 0, together witha liquid or solid insecticidal carrier therefor.

41. An insecticidal composition comprising an insecticidally eflFectiveamount of an adduct prepared by reaction ofdecachlorooctahydro-1,3,4-metheno-2H-cyclobuta (cd) pentalen-2-one and acompound having the formula in which R is a member of the groupconsisting of hydrogen and alkyl containing 1 to 3 carbon atoms, in molratio of about 0.5 to 2 mols of decachlorooctahydro-1,3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one per mol of compound, attemperature ranging from room temperature to about 250 C. together witha liquid or solid insecticidal carrier therefor.

5. A process for combatting insects which comprises subjecting theinsects to the action of an insecticidally effective amount of an adductprepared by reaction of decachloroctohydro-1,3,4-metheno 2H cyclobuta(cd) pentalen-Z-one and a compound having a formula consisting of (l)RCH COR in which R is a member of the group consisting of hydrogen andmethyl and R is a member of the group consisting of unsubstituted alkylcontaining 1 to 9 carbon atoms, arylalkyl in which the alkyl contains 1to 4 carbon atoms, haloalkyl in which the alkyl contains 1 to 4 carbonatoms, carboalkoxyalkyl in which the alkyl contains 1 to 4 carbon atomsand the alkoxy contains 1 to 4 carbon atoms, carboalkoxy in which thealkoxy contains 1 to 2 carbon atoms, phenyl and acetyl,

in which R is a member of the group consisting of hydrogen and alkylcontaining 1 to 3 carbon atoms and in which R is a member of the groupconsisting of hydrogen and alkyl containing 1 to 3 carbon atoms, in molratio of about 0.5 to 2 mols of decachlorooctahydro-1,3,4-metheno 2Hcyclobuta (cd) pentalen-2-one per mol of compound, at temperatureranging from room temperature to about 250 C.

6. A process for combatting insects which comprises subjecting theinsects to the action of an insecticidally efiective amount of an adductprepared by reaction of decachlorooctahydro-1,3,4-metheno 2H cyclobuta(cd) pentalen-Z-one and a compound having the formula RCH COR in which Ris a member of the group consisting of hydrogen and methyl and R is amember of the group consisting of unsubstituted alkyl containing 1 to 9carbon atoms, iarylalkyl in which the alkyl contains 1 to 4 carbonatoms, haloalkyl in which the alkyl contains 1 to 4 carbon atoms,carboalkoxyalkyl in which the alkyl contains 1 to 4 carbon atoms and thealkoxy contains 1 to 4 carbon atoms, carboalkoxy in which the alkoxycontains 1 to 2 carbon atoms, phenyl and acetyl, in mol ratio of about0.5 to 2 mols of decachloroctahydro-1,3,4-metheno-2H-cyclobuta (cd)pentalen-Z-one per mol of compound, at temperature ranging from roomtemperature to about 250 C.

7. A process for combatting insects which comprises subjecting theinsects to the action of an insecticidally efiective amount of an adductprepared by reaction of decachlorooctahydro-l,3,4-metheno 2H cyclobuta(cd) pentalen-Z-one and a compound having the formula in which R is amember of the group consisting of hydrogen and alkyl containing 1 to 3carbon atoms, in mol ratio of about 0.5 to 2 mols ofdecachlorooctahydro-l, 3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one permol of compound, at temperature ranging from room temperature to about250 C.

8. A process for combatting insects which comprises subjecting theinsects to the action of an insecticidally effective amount of an adductprepared by reaction of decachlorooctahydro-1,3,4-metheno 2H cyclobuta(cd) pentalen-Z-one and a compound having the formula 12 compound, attemperture ranging from room temperature to about 250 C.

9. A composition according to claim 4 wherein the auduct prepared byreaction of decachlorooctahydro-l,3.4- metheno-ZH-cyclobuta (cd)pentalen-Z-one and ethyl levulinate is employed.

10. A process according to claim 6 wherein the adduct prepared byreaction of decachlorooctahydro-L3.4- metheno-ZH-cyclobuta (ed)pentalen-Z-one and ethyl levulinate is employed.

References Cited UNITED STATES PATENTS 7/1963 Hoch et a1. 167-30 9/1967Gilbert et al. 16750 US. Cl. X.R. 424-331 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3,369,030 Dated Sept. 23, 9 9

Inventofla) J. R. Priebe It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

In Column equation (2) should be as follows:

51mm Am SEALED JAN 201970 Aneat:

Edward M. Fletcher, Ir. WILLIAM E. SGHUYLER,

.Attesting Officer Comissioner of Patent:

